2, 3, 5, 6, tetramethyl anilino anthraquinones and method of making the same



Patented May 13, 1952 w 2,3,5,6,TETRAMETHYL ANILINO ANTHRAQUI- gggiES AND METHOD OF MAKING THE James Ogilvie, Buffalo, N. Y., assignor to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application April 13, 1949, Serial No. 87,342

1 12 Claims. (Cl. 260-374) This invention relates to novel anthraquinone Vide brilliant blue, water-soluble sulfonated dyedyestufis containing aryl amino groups derived stuffs which dye proteinaceous fibers, such as from the hydrocarbon 1,2,4,5-tetramethylben- Wool and silk, and other nitrogenous fibers such acne, and to a process for preparing them. as nylon, from either an acid or neutral dye- The new dyestuffs of my invention belong to bath in strong, bright blue to bluish-green shades, the so-called milling color type and produce which possess excellent fastness to light, washpure, brilliant blue to blue-green shades upon ing and fulling, and a substantially higher neuyeing. tral afiinity to wool than has been obtained in Anthraquinone dyestufis have been well-known the past. in the past and have been applicable mainly to lo It is a still further object of this invention to dyeing cotton fibers on which'they produce brilprovide dyestuffs of the aforementioned properliant shades of excellent fastness to light and ties, which dye wool from neutral and acid dyewashing. In general, however, they are unsuitbaths without showing undue disparity in shade ed to dyeing nitrogen-containing fibers, such as and strength in the dyeings thus produced. wool, silk, nylon, etc., because of the necessity Another object of the invention is to provide for using alkaline reducing baths to dissolve the water-insoluble unsulfonated anthraquinone dyedyestufi. The alkali of these baths tends to be stuffs, which are soluble in and suitable for coldestructive or harmful to wool and other nitrooring organic solvents of the pyridine and subgen-containing fibers. stituted benzene types, and for coloring plastics Attempts in the past to dye such nitrogen and lacquers, especially those containing celcontaining fibers from neutral or acid baths lulose esters and ethers, such as cellulose acetate. have taken many forms, among which are ex- The objects of the present invention are acpedients which render the dyestuff water-soluble, complished according to my invention through as by the introduction of sulfo groups into the the provision of novel anthraquinone dyestuffs of dyestuff molecule, and the like. the following general formula:

Dyestufis of the character referred to above, Z O prepared from sulfonated compounds of the an- 1 II I thraquinone series derived from certain aromatic amines, have been known in the past. However,

dyestufis of this class which dye wool pure blue E30 0H3 shades are either deficient in fastness proper- I I ties or are not suitable for neutral dyeing. Oth- Y I NH X ers which are suitable for neutral dyeing and possess the desired fastness properties, especial- 1y fastness to washmg meld dyemgs Wmch are wherein It represents a member selected from not pure blue or brilliant in shade. Thus according to British Patent 579,519 the prior art the gmup onslstmg hydmgen' alkyl' and the dyestufi 1,4-bis (2', 4', 6'-trimethyl anilino) mdml anthraquinone disulfonate exhibits in a neutral (131% dyebath only about 25% of the afiinity to wool 40 p that it exhibits in an acid dye-bath of equal X initial dyestuff concentration which is complete- L ly exhausted. Y H1 Similarly, another type of prior art dyestuff, and each X represents a member selected from namely 1,4-bis (2', 4, 6'-triethyl anilino) anthe group consisting of hydrogen and a sulfo thraquinone disulfonate exhibits a neutral dyegroup, and Y and Z each represent a member ing afiinity to wool of only about selected from the group consisting of hydrogen It is an object of the invention to provide as andNI-IR, wherein R. has the significance defined new compositions of matter novel anthraquinone above. dyestufis containing as s'ubstituents from one to 50 The new dyestuffs of the invention which confour 6-amino-1,2,4,5-tetramethylbenzene groups, tain one or more sulfo groups, are soluble in one or more of which may be further substituted water. They are distinguished by outstanding by a sulfo group, and a process for preparing neutral dyeing aflinity to animal fibers such as such novel compositions. wool, of the order of -85%, combined with an It is a further object of the invention to 'pro- 5 ability to dye such fibers from an acid or neutral dyebath in pure blue to bluish-green shades possessing excellent brilliance and fastness properties. Dyestuffs of the invention, which are devoid of sulfo groups, are insoluble in water, but they are soluble in many organic solvents such as nitrobenzene, monochlorobenzene, dichlorobenzene, pyridine, somewhat soluble in benzene and gasoline, and are practically insoluble in ethyl alcohol. When dissolved in organic solvents, the

dyestuffs yield pure blue to bluish green colorations of good fastness properties. The dyestuffs are also suitable for coloring plastics and lacquers, such as cellulose acetate, and the-like.

The term "sulfo group as used herein is in-- tended to include both the acid group, 5031-1, and the alkali metal, e. g. sodium and potassium, and ammonium substituted groups.

The novel dyestuffs of the invention may be prepared by condensing durene, i. e. 1,2,4,5-tet* ramethylbenzene, through a nuclearly halogenated derivative thereof of the following formula? H3O CH3 halogen at ta.

with an anthraquinone compound (including leuco forms thereof) of the general formula:

B O A I. I1 I riod of between about five hours and about a twenty hours usually being sufiicient. The halogen-durene compound is preferably employed in an amount equal to or slightly in excess of one mol for each amino group to be substituted per mol amino-anthraquinone compound. The condensation is preferably carried out in the presence of a catalyst, such as a copper-containing catalyst, for example powdered copper or a copper salt, and an acid binding agent, such as alkali metal and ammonium salts, nitrogen bases, etc., for example ammonium and alkali metal acetates, carbonates and bicarbonates, urea, and the like. Where a leuco anthraquinone compound is employed, the reaction product may be converted to the anthraquinone form in customary manner by treatment with a suitable oxidizing agent, e. g. nitrobenzene, a peroxide, or aperborate. The water-insoluble condensation products thus obtained may be converted into water-soluble sulfonic acids by treatment with a sulfonating agent such as sulfuric acid or oleum of suitable concentration, mixtures of sulfuric acid and oleum,

and chlorosulfonic acid, according to methods known in the art.

Among the aminoanthraquinone compounds of the above type which may be reacted with a halogen-durene, such as, for example, l-bromo- 2,3,5,6-tetramethylbenzene, in accordance with the present invention, are included 1,4-diaminoanthraquinone', 1 methylaminol-aminoanthraquinone, 1 isopropylamino-4-amino-anthraquinone, 1-amylamino-4-aminoanthraquinone, 1,4- le'uco-diaminoanthraquinone, 1,4,5 triaminoanthraquinone, 1,4,5,8 tetraaminoanthraquinone and l,4-dirnethylamino 5,8 diaminoanthraquinone and the like.

The halogenated-durene compound (1. e. halogeriated 1,2,435-tetramethylbenzene) may be prepared by the-method described in JACS 55 (1933) pages 1680-1681, with respect to monobromodurene, which consists essentially of brominating a carbon tetrachloride solution of durene.

The following specific examples will further illustrate the invention Ewample l agitated mixture of 48 parts of monobromodurene 16 parts of 1,4-diaminoanthraquinone 40 parts of n'it'robenzene 14 parts of anhydrous potassium acetate 0.3 art of co per acetate 0.3 part of cuprous chloride is heated to 180 to 190 C. for 15 hours, during which period the reaction mixture gradually assumes a bright blue coloration. The reaction mixture is allowed to cool to 70 to C., and is mixed with 80 parts of denatured ethyl alcohol formula 23 (96% ethyl alcohol denatured with /2 gallon of benzene per 100 gallons of ethyl alcohol. U. S. Treasury Dept. Bur. of Internal Revenue' Appendix to Regulations #3-Formulae for completely and specially denatured alcohols 1942 p. 14). The diluted mixture is allowed to cool to 25 C. and filtered, and the filter cake is washed with 40 parts of alcohol 2B. The cake is boiled with 500 parts of about 2% aqueous hydrochloric acid for about /2 hour, then filtered, washed with water and dried. The dry dyestufi" base thus obtained is purified by dissolving it in 6 times its weight of hot orthodichlorobenzene, cooling the solution to crystallize the base, filtering, washing the filter cake with a little alcohol 23, and drying the washed cake.

The condensation product thus obtained has the following formula:

It is practically insoluble in ethyl alcohol, somewhat soluble in gasoline, benzene, and acetone and appreciably soluble in solvents such as pyridine, nitrobenzene and orthodichlorobenzene, yielding pure blue solutions of good fastness to 7 light.

completely soluble in hot water, The reaction mixture is then poured into 700 parts of ice cold water containing 35 parts of common salt, and the precipitated dyestuff is separated by filtration and washed acid free with 5% aqueous sodium chloride. The filter cake of dystuff sulfonic acid thus obtained is slurried in water and the slurry is rendered neutral to Brilliant Yellow with aqueous sodium carbonate, and evaporated to dryness at 100 C.

The the dyestuff thus obtained, at least one of the duryl residues contains a nuclear sulfo group, SOsNa, in the 4 position on the ring. It dyes wool from either an acid or neutral dyebath in brilliant, pure blue shades of excellent tinctorial strength and fastness properties, being notably fast to light, washing, and fulling. It is of particular value as a neutral dyeing dyestuif,

since it posseses a neutral dyeing afiinity to wool of about 85% compared with an acid dyeing obtained with a deybath of equal concentration which exhausts completely. In this respect it is considerably superior to the prior art dyestuffs:

3 IITH CH3 S 031%.

C Ha I I S OaNa NH CH3 and 21 0 h) 1711 -C2Hn S OaNa 2H5 CQHE I S OaNa NH- C2115 which, according to British Patent 579,519,

possess neutral dyeing aifinities of only 25% and 50 respectively.

Example 2 A mixture of 36 parts of monobromodurene 18 parts of leuco lA-diaminoanthraquinone 17.4 parts of anhydrous potassium acetate 1.5 parts of copper carbonate 40 parts of nitrobenzene is heated with agitation to 185 C. for 12 hours until the condensation is complete. The reaction mixture is allowed to cool overnight, then 200 parts of chlorobenzene are added and the mixture is heated to 120 C. to effect complete solution. The solution is cooled to 20 to 25 C. and filtered, and the filter cake is washed with 80 parts of denatured alcohol formula 23. The filter cake is slurried in 500 parts of about 2% hydrochloric acid, and the slurry is heated to boiling for' hour, and filtered, and the filter cake is washed and dried.

Sulfonation is efiected by adding 20 grams of 'the dyestufi base obtained above to a mixture in Example 1 6 of '74 parts of sulfuric acid and 38 parts of 26% oleum, and agitating the reaction mixture at 10 to 15 C. until a sample thereof is completely soluble in hot water (1 to 2 hours). The sulfonation mass is drowned in a solution of 265 parts of common salt in about 950 parts of water, and the precipitated dyestuff is separated by filtration, washed acid-free with 22% aqueous sodium chloride solution and then with about 300 parts of 5% aqueous sodium chloride and dried. The water-soluble dyestufi thus obtained is essentially identical with the dyestuif obtained Example 3 A mixture of llxi parts of monobromodurene 9.6 parts of 1-methylamino-4-amino-anthraquinone 24 parts of nitrobenzene 9.6 parts of potassium acetate 0.2 part of cuprous chloride 0.2 part of copper carbonate 1 equal Weight of chlorobenzene and dried.

The dyestuff base thus obtained has the following formula:

It dissolves in organic solvents to yield bright the unsulfonated dyestuif prepared inExample 1, it is generally somewhat more soluble in the aforementioned organic solvents.

The dyestuff base is sulfonated by adding 8 parts thereof to 40 parts of 100% sulfuric acid, 40 parts of 26% oleum and 3 parts of sodium sulfate at 10 to 15 C., and agitating the reaction mixture at that temperature until a sample of the mass is completely soluble in water. The sulfonation mass is worked up in the manner described in Example 1. The dyestufi thus obtained has the following formula:

(6 NBC Ha NH -S O;Na

Ha 0 H3 It dyes wool from either an acid or neutral dyebath in string, fast blue shades, which are redder and somewhat duller than those obtained with the sulfonated dyestuff of Example 1.

Example 4 A mixture of 54 parts of monobromodurene 12 parts of 1,4,5,8-tetraaminoanthraquinone 84 parts of nitrobenzene 24 parts of potassium acetate 0.5 part of cuprous chloride 0.5 part of copper carbonate is heated with agitation to 185 to 190 C. for 20 hours. The reaction mixture is cooled to 80 C., diluted with 105 parts of denatured alcohol formula 2B, and filtered, and the filter cake is washed with 50 parts of alcohol 213. The filter cake is digested with about 500 parts of about 5% sulfuric acid at the boil, filtered, washed and dried. The crude condensation product thus ob tained is purified by recrystallization from about 5 times its weight of othodichlorobenzene.

The purified dyestuff base has the following formula:

Halo ([3113 H3? 113 -HN O NH H l 1110 Es Ha!) Ha H: C ?Ha Ha C Ha Hal! one It is practically insoluble in ethyl alcohol, sparingly soluble in acetone and gasoline but appreciably soluble in solvents like nitrobenzene, pyridine and orthodichlorobenzene to yield turquoise colorations. Sulfonation of the dyesuff base with 10 times its weight of 26% oleum at 60 C. yields a water-soluble dyestuff, which may be worked up as described in Example 1 and dyes wool from an acid or neutral bath bluish-green shades. The formula of the water-soluble sulfonated dyestufi. is similar to the tetraduryl aminoanthraquinone set forth above with the substitution in at least one, and possibly up to all four of the duryl radicals of a nuclear sulfo group.

While the above describes the preferred embodiments of the invention, it will be understood that departures may be made therefrom within the scope of the specification and claims.

What is claimed is:

1. As new compositions of matter, the anthraquinone dyestufis having the following general formula:

2 o NHR I II I b NHQX H343 Ha wherein R represents a member selected from the group consisting of hydrogen, alkyl and the radical I l 3- H3 C C Ha each X represents a member selected from the group consisting of hydrogen and a sulfo group, and Y and Z each represent a member selected 8 from the group consisting of hydrogen and NHR wherein R has the same significance as above.

2. As new compositions of matter, the anthraquinone dyestufis'having the formula:

fi) NH X 10 at 6H,

nn: H;

NH- X Haf l (I311:

wherein each X is a memberselected from the group consisting of hydrogen and a sulfo group.

3. As new compositions of matter, the anthraquinone dyestuffs having the formula:

' i) NHa1kyl mo 0H3 NH X wherein X is a member selected from the group consisting of hydrogen and a sulfo group.

4. As new compositions of matter, the anthrar quinone dyestufls having the formula:

wherein each X. is a member selected from the group consisting of hydrogen and a sulfo radical.

5. In a process for preparing new anthraquinone dyestuffs having the following general formula:

wherein R. represents a member selected from the group consisting of hydrogen, alkyl and the radical H3 C CH3 each X represents a member selected from the group consisting of hydrogen and a sulfo group, and Y and Z each represent a member selected from the group consisting of hydrogen and Nl-L-R wherein R has the significance indicated 75 above, the step which comprises heating a mixture of an anthraquinone compound having the formula I NH:

wherein A represents a member selected from the group consisting of amino and 'alkylamino radicals, and B and C each represent a member selected from the group consisting of hydrogen, amino and alkylamino radicals, and 3-h'alo- 1,2,4,5-tetramethyl-benzene, to a temperature between about 100 Ceand about 250 C. in a liquid diluent and in the presence of a catalyst.

6. The process of claim 5 wherein the resulting product is treated. with a sulfonating agent.

7. The process according to claim 5 wherein the liquid diluent is a nitrated aromatic hydrocarbon, and wherein the catalyst is a coppercontaining material.

8. In a process for preparing new anthraquinone dyestuffs of the formula:

Hz? CE:

(|) NH X Hs) CHI H O CE:

I NH X H: HI

1,4-diamino anthraquinone in a, nitrobenzene solution at a temperature between about 180 C. and about 190 C. for a period of between about 5 hours and about 15 hours, in the presence of a copper-containing catalyst and an acid-binding agent. V

9. In a process for preparing new anthraquinone dyestufis of the formula:

wherein X represents a member selected from the group consisting of hydrogen and a suite groupffthe step which comprises heating a mixture containing between about 1 and about 2 molecular proportions of 1,2,4,5-tetramethyl-3- broinobenzene per mol of a 1-amino-4-alky1- amino-anthraquinone in a nitrobenzene solution at a temperature between about C. and about" C. for a period between about 5 hours and about 20 hours in the presence of a coppercontai ning catalyst and an acid-binding agent.

10. a process for preparing new anthraquinone dyestufis of the formula:

wherein X represents a member selected from the group consisting of hydrogen and a sulfo group, the step which comprisesheating a mixture containing at least about four mols of 1,2,4,5 tetramethyl-3-bromobenzene and about one mol of 1,4,5,8-tetraaminoanthraquinone dissolved in nitrobenezne, to a temperature between about 180 C. and about 190 C. for between about 5 and about 20 hours in the presence-0t a. copper-containing catalyst and an acid binding agent.

11. The composition of claim 1 wherein each X is hydrogen.

12. .The composition of claim 1 wherein at least one X is a sulfo group. JAMES OGILVIE.

REFERENCES CITED The following references are or record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,253,828 von Allmen et a1. Aug. 26, 1941 FOREIGN PATENTS Number Country Date 579,519 Great Britain Aug. 7, 1946 

1. AS NEW COMPOSITIONS OF MATTER, THE ANTHRAQUINONE DYESTUFFS HAVING THE FOLLOWING GENERAL FORMULA: 